This paper reports an investigation on the role of coexposed TiO2's (001) and (101) facets on the performance of TiO2/BiVO4 photoanodes in the photocatalytic fuel cell. Here, the exposure of these facets was obtained by synthesizing TiO2 with different morphologies, i.e. nanospindles, nanocube, nanooctahedra and nano-truncated octahedra. Based on the result, coexposed (001) and (101) facets were found to be responsible for the enhancement of photoelectrochemical response. The highest photocurrent density was achieved when the photoanode was fabricated using TiO2 nano-truncated octahedra/BiVO4 (29.8 μA/cm2 at 0.8 V vs. NHE), which was primarily due to the improvement of charge separation as a result of the synergistic effect between the formation of type-II heterojunction of TiO2/BiVO4 and internal surface heterojunction of (001) and (101) facet. A similar trend was also observed in the PFC system when RhB was used as fuel. Under the illumination of 13 W LED light, the highest electric power (0.00232 mW/cm2) was obtained with TiO2 nano-truncated octahedra/BiVO4 photoanode. However, TiO2 nanospindles/BiVO4 was found to be more effective in removing RhB due to its high surface area. Such variation was believed due to the fact that TiO2 nanospindles had less exposure of (001) facet than TiO2 nano-truncated octahedra.